Anthraquinoylcarboxylic acid hydrazides, curable compositions and use thereof

ABSTRACT

Anthraquinones of formula I ##STR1## wherein X is the group --CR 2  R 3  --, where R 2  is H, --CH or C 1  -C 5  -alkyl and R 3  is H or --CN, R 1  is H or C 1  -C 5  -alkyl and R is a direct bond or linear or branched C 1  -C 18  -alkylene which, alone or together with the --CR 2  R 3  -- group, can be interrupted by one or more --O-- when R 2  and/or R 3  are not --CN, and curable compositions comprising (a) an epoxy resin, (b) a hardener if necessary, (c) an anthraquinone of formula I and (d) an amino alcohol. The cured compositions are photosensitive and are suitable for the preparation of coatings and metallic images by electroless metal deposition.

This is a divisional application Ser. No. 208,522 filed on June 20, 1988now U.S. Pat. No. 4,855,094.

The invention relates to anthraquinoylcarboxylic acid hydrazides, to acurable composition consisting of (a) an epoxy resin, (b) a hardener ifnecessary, (c) an anthraquinonecarboxylic acid hydrazide and (d) anamino alcohol, and to the use thereof for the preparation of metalliccoatings or images.

European patent application No. A-0 112 798 proposes photosensitivecrosslinked reaction products based on epoxy resins. With theconcomitant use of metal salts of groups Ib and VIII of the periodictable of the elements, metal nuclei can be produced by exposure to lightand these can be increased by electroless metal deposition. It isdesirable to produce metallic coatings or images, by electroless metaldeposition, direct on photosensitive epoxy resins without theconcomitant use of metal salts.

The invention relates to anthraquinones of formula I ##STR2## wherein Xis the group --CR² R³ --, where R² is H, --CN or C₁ -C₅ -alkyl and R³ isH or --CN, R¹ is H or C₁ -C₅ -alkyl and R is a direct bond or linear orbranched C₁ -C₁₈ -alkylene which, alone or together with the --CR² R³ --group, can be interrupted by one or more --O-- when R² and/or R³ are not--CN.

The group ##STR3## is preferably bonded in the 2-position of theanthraquinone.

In a preferred embodiment of the invention, the anthraquinones offormula I are those wherein X is the group --CR² R³ -- in which R² is Hor C₁ -C₅ -alkyl and R³ is H. Those in which R² and R³ are both H areespecially preferred.

R¹ and R² can be linear or branched alkyl; alkyl is preferably e.g.methyl or ethyl. R¹ is preferably H or methyl. R as alkylene may bebranched or, preferably, linear. It preferably contains 1 to 12,especially 1 to 8, C atoms.

In another preferred embodiment of the invention, X is --CH₂ -- and R isa direct bond or a linear alkylene having 1 to 8 C atoms.

R as alkylene may be interrupted by --O--, preferably by 1 to 4,especially 1 to 2, --O--. In a preferred embodiment of the invention,the alkylene interrupted by --O-- has the formula --C_(m) H_(2m)--O--_(y), wherein m is a number from 2 to 4, preferably 2 to 3 andespecially 2, and y is a number from 1 to 6, preferably 1-4 andespecially 1 or 2.

According to U.S. Pat. No. 2,884,424, anthraquinone-2-carboxylic acidhydrazide can only be prepared by reacting an appropriate ester with anexcess of hydrazine to give the leuco form and then oxidizing thelatter. It has been found, surprisingly, that the anthraquinones of theinvention are formed direct when alcoholic solutions of the appropriateesters are reacted with hydrazine.

The invention further relates to a process for the preparation ofanthraquinones of formula I, wherein an anthraquinonecarboxylic acidester of formula II ##STR4## wherein X and R are as defined above or thegroup --XR-- is a direct bond and R⁴ O-- is the radical of an alcohol,is reacted in the presence of an alcohol with a hydrazine of formula III

    HNR.sup.1 NH.sub.2                                         (III),

wherein R¹ is as defined above, or with the hydrate or salts thereof.

R⁴ in formula II is preferably C₁ -C₆ -alkyl and especially C₁ -C₄-alkyl. R⁴ is, in particular, methyl or ethyl.

The alcohol is preferably an alkanol having, in particular, 1-4 C atoms.It is preferred to use alkanols whose alkyl radical is identical withR⁴. The use of ethanol is especially preferred.

The reaction is advantageously carried out under an inert gasatmosphere. The reaction temperature can be 30° to 180° C. and ispreferably 50° to 120° C.

The alkanol can serve as solvent. Other inert solvents can additionallybe used, e.g. ethers (diethyl ether, dioxane, tetrahydrofuran),cellosolve, sulfoxides and sulfones, and N-alkylated acid amides.

The hydrazines of formula III are known. Hydrazine hydrate isadvantageously used. Salts can be derived e.g. from mineral orcarboxylic acids.

The esters of formula II are known or can be prepared by processes knownper se. Japanese patent disclosure No. Sho 55/89245 proposes thepreparation of (anthraquino-2-yl)acetic acid esters by the substitutionof anthraquinoyl chloride with malonic acid diesters. Malonitrile andmalonic ester-nitriles can be used analogously. The anthraquinoylmalonicderivatives obtainable in this way can be reacted in known manner withC₁ -C₅ -alkyl halides or with carbalkoxyalkyl halides. Partialhydrolysis of the nitrile or ester groups and, in some cases,decarboxylation gives further esters of formula II after esterification.These reactions can also be carried out with the knownanthraquinoylacetonitrile.

The esters of formula II can also be obtained by the known reaction ofanthracene with alkenecarboxylic acid esters and subsequent oxidatione.g. with Jones reagent. A further possibility is stepwise synthesisinvolving the reaction of phenalkylcarboxylic acid esters, known per se,with phthalic anhydride, subsequent cyclization to theanthraquinonealkanecarboxylic acid and esterification thereof.Phenalkylcarboxylic acid esters can also be obtained by the catalytichydrogenation of benzoylalkanecarboxylic acids and simultaneous orsubsequent esterification.

Esters of formula II wherein R is alkylene interrupted by --O-- can beprepared by first reacting a halogenoalkylanthraquinone with analkylenediol and then, in some cases, with alkylene oxides. The hydroxylcompounds obtained can then be reacted with alkenecarboxylic acid estersor halogenoalkylcarboxylic acid esters.

The compounds of formula I are suitable for the preparation ofphotosensitive cured epoxy resins. The invention further relates to acurable composition comprising

(a) at least one epoxy resin with an average of more than one epoxygroup in the molecular,

(b) an epoxy resin hardener if necessary,

(c) at least one anthraquinone of formula I, the group --XR--additionally being a direct bond, and

(d) at least one primary or secondary aliphatic amine containing atleast one hydroxy group in the aliphatic radical.

The preferences mentioned previously apply to the compounds of formulaI.

The epoxy resin preferably contains an average of at least 2 epoxygroups in the molecule.

Possible epoxy resins are, in particular, those with an average of morethan one glycidyl group, β-methylglycidyl group or 2,3-epoxycyclopentylgroup bonded to a heteroatom (e.g. sulfur, preferably oxygen ornitrogen); these are, in particular, bis(2,3-epoxycyclopentyl) ether;diglycidyl or polyglycidyl ethers of polyhydric aliphatic alcohols suchas butane-1,4-diol, or polyalkylene glycols such as polypropyleneglycols; diglycidyl ethers of cycloaliphatic polyols such as2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl or polyglycidyl ethersof polyhydric phenols such as resorcinol, bis(p-hydroxyphenyl)methane,2,2-bis(p-hydroxyphenyl)propane (=diomethane),2,2-bis(4'-hydroxy-3',5'-dibromophenyl)propane and1,1,2,2-tetrakis(p-hydroxyphenyl)ethane, or of condensation products ofphenols with formaldehyde which are obtained under acid conditions, suchas phenol novolaks and cresol novolaks; di(β-methylglycidyl) orpoly(β-methylglycidyl) ether of the abovementioned polyhydric alcoholsor polyhydric phenols; polyglycidyl esters of polybasic carboxylic acidssuch as phthalic acid, terephthalic acid, Δ⁴ -tetrahydrophthalic acidand hexahydrophthalic acid; N-glycidyl derivatives of amines, amides andheterocyclic nitrogen bases, such as N,N-diglycidylaniline,N,N-diglycidyltoluidine, N,N,O-triglycidyl-p-aminophenyl andN,N,N',N'-tetraglycidyl-bis(p-aminophenyl)methane; triglycidylisocyanurate; N,N'-diglycidylethyleneurea;N,N'-diglycidyl-5,5-dimethylhydantoin,N,N'-diglycidyl-5-isopropylhydantoin,N,N-methylene-bis(N',N'-diglycidyl)-5,5-dimethylhydantoin and1,3-bis(N-glycidyl- 5,5-dimethylhydantoin)-2-glycidyloxypropane; andN,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil.

Glycidylated novolaks, hydantoins, aminophenols, bisphenols or aromaticdiamines are a preferred group of epoxy resins. Especially preferredcompositions contain, as epoxy resin, a glycidylated cresol novolak,bisphenol A diglycidyl ether, bisphenol A diglycidyl ether "advanced"with bisphenol A, hydantoin N,N'-bisglycide,2-hydroxypropylene-1,3-bishydantoin triglycide, p-aminophenoltriglycide, diaminodiphenylmethane tetraglycide or mixtures thereof.

Prereacted adducts of such epoxides with epoxy hardeners are alsosuitable, e.g. the above-mentioned adduct of bisphenol A diglycidylether and bisphenol A.

Possible epoxy resin hardeners are acidic or basic compounds. Examplesof suitable hardeners are: amines such as aliphatic, cycloaliphatic oraromatic, primary, secondary and tertiary amines, e.g. ethylenediamine,hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine,N,N-dimethylpropylene-1,3-diamine, N,N-diethylpropylene-1,3-diamine,2,2-bis(4'-aminocyclohexyl)propane,3,5,5-trimethyl-3-(aminomethyl)cyclohexylamine ("isophoronediamine") andMannich bases such as 2,4,6-tris(dimethylaminomethyl)phenol;m-phenylenediamine, p-phenylenediamine, bis(4-aminophenyl)methane,bis(4-aminophenyl) sulfone and m-xylylenediamine; adducts ofacrylonitrile or monoepoxides, e.g. ethylene oxide or propylene oxide,and polyalkylenepolyamines, e.g. diethylenetriamine ortriethylenetetramine; adducts of an excess of polyamines, e.g.diethylenetriamine or triethylenetetramine, and polyepoxides, e.g.diomethane polyglycidyl ethers; adducts of monophenols or polyphenolsand polyamides; polyamides, in particular those derived from aliphaticpolyamines, e.g. diethylenetriamine or triethylenetretramine, anddimerized or trimerized unsaturated fatty acids, e.g. dimerized linoleicacid (VERSAMID®); polysulfide (THIOKOL®); aniline-formaldehydes;polyhydric phenols, e.g. resorcinol, 2,2-bis(4-hydroxyphenyl)propane orphenolformaldehyde resins; polybasic carboxylic acids and theiranhydrides, e.g. phthalic anhydride, Δ⁴ -tetrahydrophthalic anhydride,hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride,3,6-endomethylene-Δ⁴ -tetrahydrophthalic anhydride,4-methyl-3,6-endomethylene-Δ⁴ -tetrahydrophthalic anhydride(=methylnadic anhydride), 3,4,5,6,7-hexachloro-3,6-endomethylene-Δ⁴-tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride,trimethyladipic anhydride, azelaic anhydride, sebacic anhydride, maleicanhydride and dodecylsuccinic anhydride; and pyromellitic dianhydride,trimellitic anhydride, benzophenonetetracarboxylic dianhydride ormixtures of such anhydrides.

Novolaks, polyamines and carboxylic acid anhydrides are a preferredgroup of hardeners.

The composition of the invention can also contain curing acceleratorsand/or polymerization initiators or thermal and/or photochemical curingcatalysts. Examples are: tertiary amines, salts thereof or quaternaryammonium compounds, e.g. 2,4,6-tris(dimethylaminomethyl)phenol,benzyldimethylamine, 2-ethyl-4-methylimidazole and triamylammoniumphenate; or alkali metal alcoholates, e.g. sodium hexanetriolate;monophenols or polyphenols such as phenol, diomethane or salicylic acid;dicyandiamide; boron trifluoride and its complexes with organiccompounds, such as BF₃ -ether complexes and BF₃ -amine complexes, e.g.BF₃ -monoethylamine complex and acetoacetanilide-BF₃ complex; phosphoricacid; and triphenyl phosphite. Suitable photochemical curing catalystsare onium salts or metal complex salts, e.g. diazonium salts of aromaticamines, triphenylsulfonium or diphenyliodonium salts orcyclopentadienyl-iron-arene salts.

Curing accelerators and catalysts are conventionally added in an amountof 0.1-10% by weight, based on the epoxy resin. Epoxy resin hardenersare generally used in equimolar amounts, based on the epoxy groups andfunctional groups of a hardener.

The composition preferably contains the anthraquinone of formula I in anamount of 0.1-1, especially 0.2-0.8, mol/kg of epoxy resin, and theamine containing hydroxyl groups in an amount of 0.1-1.2, especially0.3-1, mol/kg of epoxy resin. Additional hardeners are preferablypresent in an amount of 0.1-0.5, especially 0.1-0.3, mol/kg of epoxyresin.

The amines of component (d) can be aliphatic amines containing hydroxylgroups, having 2 to 30, preferably 2 to 20, C atoms and having 1 to 3,preferably 1, hydroxyl group in the aliphatic radical. The aliphaticradical can be linear or branched and interrupted by --O-- or aminogroups. The aliphatic radical preferably contains primary OH groups. Ina preferred embodiment of the invention, the amine has the formula IV##STR5## wherein R⁵ is H, linear or branched C₁ -C₁₈ -alkyl, C₃ -C₇-cycloalkyl, C₆ -C₁₀ -aryl, C₇ -C₁₈ -alkaryl, C₇ -C₁₂ -aralkyl, C₈ -C₁₈-alkaralkyl or the group --C_(y) H_(2y+1-x) OH_(x), x is a number from 1to 3 and y is a number from 2 to 12, it being possible for the groupC_(y) H_(2y) to be interrupted by one or more --O-- or --NR⁵ --.

R⁵ as alkyl preferably contains 1 to 12 and especially 1 to 6 C atoms.R⁵ as alkyl is preferably methyl or ethyl. R⁵ is H in particular. R⁵ ascycloalkyl preferably contains 5 or 6 ring C atoms and is e.g.cyclopentyl or cyclohexyl.

R⁵ as aryl may be naphthyl and especially phenyl. R⁵ as alkaryl isespecially C₇ -C₁₈ -alkylphenyl, for example methylphenyl, ethylphenyl,dimethylphenyl, n- and i-propylphenyl, n-, i- and t-butylphenyl,pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl anddodecylphenyl. R⁵ as aralkyl can be 1- or 2-phenyleth-1-yl or especiallybenzyl. R⁵ as alkaralkyl is preferably alkylbenzyl having, inparticular, 8 to 14 C atoms, e.g. methylbenzyl, ethylbenzyl,dimethylbenzyl, n- and i-propylbenzyl, n-, i- and t-butylbenzyl,pentylbenzyl and hexylbenzyl. If the group C_(y) H_(2y) is interruptedby --O--, it can be an oxaalkylene radical which can have e.g. theformula --R⁶ --(OR⁷)_(t) --, wherein R⁶ and R⁷ independently of oneanother are linear or branched C₂ -C₆ -alkylene and t is a number from 2to 6. If the group C_(y) H_(2y) is interrupted by --NR⁵ --, itpreferably has the formula --R⁸ -NH)_(s) R⁹ --, wherein R.sup. 8 islinear or branched C₂ -C₆ -alkylene, preferably ethylene, R⁹ is linearor branched C₁ -C₁₀ -alkylene, preferably C₂ -C₆ -alkylene, and s is anumber from 1 to 3. In formula IV, y is especially a number from 2 to 7.

Those amines of formula IV in which R⁵ is H, y is a number from 2 to 7and x is a number from 1 to 3 are a preferred subgroup.

Examples of amines of formula IV are: ethanolamine,1-amino-2-hydroxypropane, 1-amino-3-hydroxypropane,1-amino-4-hydroxybutane, 1-amino-5-hydroxypentane,1-amino-6-hydroxyhexane, aminotrimethylolmethane,aminodimethylolmethane, aminomethyldimethylolmethane,aminomethyltrimethylolmethane, hydroxyethoxyethylamine,hydroxypropoxyethylamine, N-(hydroxyethyl)ethylenediamine,N-(hydroxyethyl)diethylenetriamine and H₂ N(CH₂ CH₂ O)₂₋₆ H.

Primary aliphatic amines containing hydroxyl groups are epoxy resinhardeners, linear polymers being obtained when epoxy resins having 2epoxy groups are used. The concomitant use of other hardeners givescrosslinked polymers.

When using the monofunctional anthraquinones of formula I, it isadvantageous to use epoxy resins having at least 3 epoxy groups in themolecule, e.g. epoxidized novolaks, in order to obtain crosslinked epoxyresins.

The compositions of the invention are curable, the cured or crosslinkedepoxy resins being photosensitive. Thin layers of metals such as coppercan be deposited by electroless metal deposition on those parts of thesurface which have been exposed to light.

The composition is cured in known manner, it being possible for curingto be preceded or accompanied by moulding in accordance with theconventional moulding processes, examples being the preparation ofcoatings on a base material by spraying, painting or knife coating, thepreparation of mouldings by means of casting techniques or thepreparation of compositions by means of dip-coating and compressionprocesses.

The anthraquinone of formula I can be prereacted with an epoxy resin togive adducts, which can then be cured with the amine containing hydroxylgroups and, if necessary, with a hardener.

The concomitant use of an epoxy resin hardener, especially a novolak,amine or anhydride hardener, may be advantageous. It is advisable toprereact the monofunctional anthraquinone together with the aminecontaining --OH and with the epoxide and then to mix the reactionproduct with a hardener and cure the mixture.

In addition to stepwise curing, it is also possible to mix all thecomponents and then cure the mixture.

The components are mixed by conventional processing methods, togetherwith a solvent if necessary. It is possible to introduce other additivesconventionally used for processing or improving the properties of thecured epoxy resins, e.g. plasticizers, dyes, pigments, fillers, mouldrelease agents or H donors. For metal deposition, metal salts or metalcomplexes of groups Ib or VIII of the periodic table of the elements mayadvantageously be present, e.g. in an amount of 0.01 to 10% by weight,based on the composition.

Curing is generally carried out at temperatures from 20° to 200° C. andespecially 50° to 150° C.

The invention further relates to the cured compositions.

The cured compositions are photosensitive. The parts exposed to lightappear darker than the unexposed parts. Metals can be deposited directon the exposed parts with conventional metal deposition baths (see e.g.U.S. Pat. No. 4,510,279), especially those containing e.g. nickel orcopper salts. Printed circuits, for example, can be prepared in thisway. The exposed epoxy resins can also be used for optical storage.

The invention further relates to the use of a cured composition of theinvention for the preparation of metallic coatings or images byelectroless metal deposition after complete or partial exposure of thesurface.

Exposure is preferably effected with UV light. Any desired light sourcescan be employed, the use of UV lamps being preferred. Examples ofsuitable light sources are xenon lamps, metal halide lamps andespecially high-pressure and medium-pressure mercury vapour lamps.

A possible procedure for preparing the metallic coatings or images is tocure the composition of the invention, which, according to theinvention, may be in the form of a layer on a base material, then toexpose it over the surface or through a master and finally to treat itwith a metal deposition bath.

The concomitant use of a metal salt or metal complex is superfluous. Thedeposited metals adhere firmly to the surface of the epoxy resin; nopretreatment is necessary. Furthermore the cured compositions have highglass transition temperatures.

The following Examples illustrate the invention in greater detail.

(A) PREPARATION EXAMPLES Example 1 Anthraquinone-2-carboxylic acidhydrazide

A mixture of ethyl anthraquinone-2-carboxylate (4.83 g) 25 ml ofethanol, 50 ml of dioxane and 7 ml of hydrazine hydrate is boiled underargon for 48 hours. It is poured into water and the product is isolatedby filtration and dried at 60° C. in a vacuum oven. Crystallization ofthe crude product (4.05 g) from dimethylformamide/chloroform gives 3.01g of product with a melting point (m.p.) of 250° C./decomposition.

Mass spectrum (indirect sample feed, 195° C.): m/e=(M³⁰, 20%), 235(100%).

EXAMPLE 2 (Anthraquino-2-yl)acetic acid hydrazide

14.7 g of ethyl (anthraquino-2-yl)acetate are dissolved in 500 ml ofabsolute ethanol, with heating. After the addition of 10 ml of hydrazinehydrate, the solution is refluxed for 20 hours. A further 10 ml ofhydrazine hydrate are added and boiling is continued for 20 hours. Themixture is filtered hot and the material on the filter is washed with50% aqueous ethanol. Crystallization of the crude product (12.5 g) from300 ml of dimethylformamide gives 11.2 g of product with an m.p. above300° C.

Analysis (% by weight): Calculated: C 68.57, H 4.32, N 10.00, O 17.13%.Found: C 68.9, H 4.4, N 9.8, O 17.2%.

EXAMPLE 3 3-(Anthraquino-2'-yl)propionic acid hydrazide (a) Diethyl(anthraquino-2-yl)malonate

48.53 g (200 mmol) of 2-chloroanthraquinone, 160.17 g (1 mol) of diethylmalonate and 500 ml of dimethyl sulfoxide (DMSO) are heated at 120° C.until everything has dissolved. The solution is then cooled to 110° C.and 165.85 g (1.2 mol) of potassium carbonate are added in portions.After stirring for 1 day at 110° C., the mixture is cooled, treated withHCl solution and extracted three times with toluene. The extracts arewashed three times with water, dried over sodium sulfate and evaporated.Filtration with toluene over silica gel and recrystallization frommethylene chloride/pentane yields 38.53 g (53%) of pure product with amelting point of 114°-117° C.

Elemental analysis (% by weight): Calculated: C 68.85, H 4.95, O 26.20%.Found: C 68.77, H 5.14, O 25.89%.

(b) Diethyl 2-(anthraquino-2'-yl)-2-carboethoxysuccinate

20.0 g (54.6 mmol) of compound (3a) are stirred with 22.63 g (164 mmol)of potassium carbonate, 18.23 g (109.2 mmol) of ethyl bromoacetate and200 ml of DMSO for 1 hour at 25° C. The mixture is treated with tolueneand dilute HCl solution. Extraction of the aqueous phase twice withtoluene, washing of the toluene phases with water, drying over sodiumsulfate and evaporation yields a crystalline residue which, afterstirring with diethyl ether, filtration and drying, gives 19.77 g (80%)of pure product with a melting point of 80°-84° C.

Elemental analysis (% by weight):

Calculated: C 66.36, H 5.35, O 28.29%.

Found: C 66.65, H 5.40, O 28.54%.

(c) (Anthraquino-2-yl)succinic acid

16.35 g (292 mmol) of potassium hydroxide are dissolved in 400 ml ofabsolute ethanol and 22.0 g (48.6 mmol) of compound (3b) are added. Themixture is stirred for 20 minutes at 25° C. and then heated to thereflux temperature over a period of 30 minutes. After cooling, it istreated with 2N aqueous HCl solution and extracted with THF/toluene(1:1). The organic phases are dried over sodium sulfate and evaporated.Stirring with diethyl ether, filtration and drying yields 15.51 g (98%)of pure product with a melting point of 245°-250° C. (decomposition).

Elemental analysis (% by weight): Calculated: C 66.67, H 3.73, O 29.60%.Found: C 66.98, H 4.02, O 28.83%.

(d) 3-(Anthraquino-2'-yl)propionic acid

10 g of dicarboxylic acid (c) are heated in 70 ml of quinoline for 5hours at 140° C. under argon. The mixture is poured into 400 ml of icewater, acidified with 2N hydrochloric acid and filtered. The material onthe filter is washed with water, dried (7.9 g) and recrystallized from300 ml of glacial acetic acid. Yield: 5.3 g; m.p.: 251° C.

Elemental analysis (% by weight): Calculated: C 72.85, H 4.32, O 22.83%.Found: C 72.2, H 4.3, O 23.4%.

(e) Ethyl 3-(Anthraquino-2'-yl)propionate

5 g of acid (3d) are refluxed in 80 ml of ethanol with 3 ml ofconcentrated sulfuric acid for 5 hours. The mixture is allowed to cool,the crystallized product is isolated by filtration and washed with 50%aqueous ethanol and the ester (4.3 g) is purified by crystallizationfrom 100 ml of ethanol. Yield: 3.7 g; m.p.: 101° C.

Elemental analysis (% by weight): Calculated: C 74.02, H 5.23, O 20.76%.Found: C 73.9, H 5.3, O 20.8%.

(f) 3-(Anthraquino-2'-yl)propionic acid hydrazide

9.2 g of ester (e) are heated in 200 ml of ethanol with 6 ml ofhydrazine hydrate for 72 hours under argon. The mixture is filtered hotand the material on the filter is washed with ethanol and 50%ethanol/water. The crude product (4.6 g) is recrystallized from 200 mlof dioxane. Yield: 3.7 g; m.p.: 229° C./decomposition.

Elemental analysis (% by weight): Calculated: C 69.38, H 4.80, N 9.52, O16.31%. Found: C 68.9, H 4.9, N 9.5, O 16.6%.

EXAMPLE 4 10-(Anthraquino-2'-yl)decanoic acid hydrazide (a) Ethyl10-phenyldecanoate

A solution of 26.15 g of 9-benzoylnonanoic acid in 260 ml of glacialacetic acid and 1 ml of 0.1N hydrochloric acid is hydrogenated (normalpressure) at 30°-35° C. with 2.6 g of palladium-on-charcoal (5% byweight) as catalyst. When no more hydrogen is taken up, the mixture isfiltered and the filtrate is evaporated under reduced pressure. Theresidue is dissolved in 200 ml of ethanol and 2 ml of concentratedsulfuric acid and the solution is refluxed for 22 hours. The solvent isevaporated off and the residue is treated with water and extracted withether. The organic phase is separated off, washed with water, sodiumbicarbonate solution (10% by weight) and saturated sodium chloridesolution, dried and evaporated. Distillation of the residue under highvacuum (1 mbar, 137°-141° C.) gives 20 g of ethyl 10-phenyldecanoate.

(b) 2-[4'-(9"-Ethoxycarbonylnonyl)benzoyl]benzoic acid

At 0°-3° C., 9.6 g of phthalic anhydride are added to a solution of 18 gof ethyl 10-phenyldecanoate in 100 ml of 1,2-dichloroethane, after which26 g of aluminium chloride are added in portions over a period of 1hour. After stirring for 20 hours at room temperature, the mixture ispoured onto ice/2N hydrochloric acid and extracted with methylenechloride. Washing of the organic phase with saturated sodium chloridesolution, drying and evaporation gives 25.1 g of2-[4'-(9"-ethoxycarbonylnonyl)benzoyl]benzoic acid as a waxy solid whichcan be used for the next step without purification.

(c) 10-(Anthraquino-2'-yl)decanoic acid

12.7 g of 2-[4'-(9"-ethoxycarbonylnonyl)benzoyl]benzoic acid are addedunder argon to 120 ml of 10% oleum preheated to 90° C. and the mixtureis stirred for 1 hour at 90° C. It is poured into 400 ml of ice waterand filtered. The material on the filter is suspended with water andtaken up in ethyl acetate. Drying of the organic phase, evaporation andcrystallization of the residue (7.2 g) from ethyl acetate gives 4.1 g of10-(anthraquino-2'-yl)decanoic acid with an m.p. of 135°-137° C. Massspectrum (indirect sample feed, 210° C.): m/e=378 (M⁺, 40%), 222 (100%).

(d) Ethyl 10-(anthraquino-2'-yl)decanoate

A solution of 4 g of 10-(anthraquino-2'-yl)decanoic acid in 80 ml ofethanol and 3 ml of concentrated sulfuric acid is refluxed for 24 hours.It is cooled to 0° C. and filtered and the product is washed withaqueous ethanol (30%). Crystallization of the material on the filterfrom methanol gives 3.7 g of product with an m.p. of 81° C.

Elemental analysis (% by weight): Calculated: C 76.82, H 7.44, O 15.47%.Found: C 76.7, H 7.4, O 15.8%.

(e) 10-(Anthraquino-2'-yl)decanoic acid hydrazide

A solution of 20 g of ester (d) in 400 ml of ethanol is refluxed for 24hours after the addition of 10 ml of hydrazine hydrate. 15 ml ofhydrazine hydrate are added and the mixture is boiled for a further 24hours. It is filtered hot and the filtrate is concentrated byevaporation of the solvent and filtered again. Crystallization of thematerial on the filter (16.7 g) from 350 ml of dioxane gives 12.6 g ofproduct with an m.p. of 190°-191° C.

Elemental analysis (% by weight): Calculated: C 73.44, H 7.19, N 7.14, 012.23%. Found: C 73.7, H 7.4, N 7.1, 0 12.3%.

Example 5 10-(Anthraquino-2'-yl)decanoic acid N-1-methylhydrazide 1.26 gof 4-methylmorpholine and 1.5 g of isobutyl chloroformate are added at-15° C. under argon to a suspension of 3.8 g of10-(anthraquino-2'-yl)decanoic acid in 40 ml of tetrahydrofuran. Afterstirring for 5 minutes at -15° C., the resulting solution is treatedwith 0.92 g of N-methylhydrazine in 10 ml of tetrahydrofuran. Themixture is stirred for 30 minutes at room temperature, the precipitatedsalts are filtered off, the solvent is evaporated off, the residue istaken up in 50 ml of ethyl acetate and the resulting solution is washedwith 20 ml of aqueous sodium bicarbonate solution (5% by weight). Theresidue of the organic phase (3.3 g) is chromatographed on 500 g ofsilica gel with chloroformethyl acetate (7:1). Crystallization of theeluate (2.8 g) from toluene gives 1.03 g of product with an m.p. of66°-67° C.

Elemental analysis (% by weight): Calculated: C 73.86, H 7.44, N 6.89, 011.81%. Found: C 74.4, H 7.5, N 6.4, 0 11.4%.

Example 6 3-[(Anthraquino-2'-ylmethoxy)ethoxy]propionic acid hydrazide(a) 2-(2'-Hydroxyethoxy)methylanthraquinone

A suspension of 10.14 g of 2-chloromethylanthraquinone in 50 ml ofethylene glycol is stirred for 14 hours at 160° C. It is taken up inchloroform and the resulting solution is washed with water and saturatedsodium chloride solution. Crystallization of the residue of the organicphase (12 g) from toluene gives 9.0 g of2-(2'-hydroxyethoxy)methylanthraquinone with an m.p. of 129°-130° C.

(b) Methyl 3-[(anthraquino-2'-ylmethoxy)ethoxy]propionate

A mixture of 264 mg of compound (a), 370 mg of potassium carbonate and 1ml of methyl acrylate in 5 ml of dimethyl sulfoxide is stirred for 2days at room temperature under argon. It is diluted with water andextracted with chloroform, the organic phase is dried and the solventsare distilled off. Chromatography of the residue on silica gel withmethylene chloride/ethyl acetate (10:1) as the eluent gives 137 mg ofproduct. Mass spectrum (indirect sample feed, 190° C.): m/e=368 (M⁺,30%), 87 (100%).

(c) 3-[(Anthraquino-2'-ylmethoxy)ethoxy]propionic acid hydrazide

A solution of 43 mg of methyl ester (b) and 0.1 ml of hydrazine hydratein 3 ml of ethanol is refluxed for 20 hours. It is diluted withmethylene chloride and washed with water and saturated sodium chloridesolution, the organic phase is dried and the solvent is evaporated off.Chromatography on silica gel with methylene chloride/ethanol (12:1) asthe eluent gives 10 mg of hydrazide. Mass spectrum (indirect samplefeed, 220° C.): m/e=368 (M⁺, 10%), 221 (100%).

(B) APPLICATION EXAMPLES Examples 7-10

11.91 g of bisphenol A diglycidyl ether and 4.95 g of10-(anthraquino-2'-yl)decylcarboxylic acid hydrazide are heated to 180°C. under inert gas, with mechanical stirring, affording a viscous, clearyellow melt. The epoxy equivalent of the melt is 2.18 mol of epoxide/kg(determined by the method of R. R. Jay, Analytical Chemistry 36 (1964)667).

The melt is dissolved in 40 ml of N-methylpyrrolidone and treated with1.13 g of propan-1-ol-3-amine and 1.23 g of a phenolformaldehyde novolakwith a hydroxy equivalent of 123.15 g/mol of OH.

The solution is cast as a film on aluminum or a polyester base by thewire-coating technique, dried in a forced-air oven for 12 hours at 80°C. and then cured at 140° C. for 4 hours.

An analogous procedure is followed in Example 8. Examples 9 and 10 arecarried out in solution, as described below for Example 9.

8.41 g of 3-(anthraquino-2'-yl)propionic acid hydrazide and 23.82 g ofbisphenol A diglycidyl ether are heated to 120° C. in 50 ml ofN-methylpyrrolidone under inert gas, with mechanical stirring, affordinga viscous, clear yellow solution. This is allowed to cool, 2.25 g ofpropan-1-ol-3-amine and 1.23 g of a cresol-formaldehyde novolak with ahydroxy equivalent of 123.15 g/mol of OH are added and the mixture isstirred at room temperature. The solution is cast as a film on aluminumor a polyester base by the wire-coating technique, dried in a forced-airoven for 12 hours at 80° C. and then cured at 140° C, for 4 hours.

Table 1 shows the composition and properties of the cured resins.

The efficiency of photoreduction is determined in the following manner.A film on a polyester base with an optical density (O.D.) of 1 at 324 nmis irradiated with a high-pressure Hg vapour lamp at 40 mW/cm⁻² and theUV/VIS spectrum is run at regular intervals. The band at 324 nmdecreases and the band at 386 nm increases. The ratio of the two bandsafter an exposure time of 2 minutes is taken as the efficiency.

Photometallization

Films on a polyester base are exposed on a thermostatically controllablevacuum heating stage at 50° C. through a negative with a high-pressureHg vapour lamp at an intensity of 40 mW/cm⁻². This affords a darknegative image of the master, which is intensified at 45° C. in adeposition bath of the following composition (see U.S. Pat. No.4,510,276):

    ______________________________________                                        CuSO.sub.4.5H.sub.2 O  0.0665 mol/l                                           HCHO                   0.0467 mol/l                                           Quadrol                0.0599 mol/l                                           NaOH                   pH 12.6                                                NaCN                   25 mg/l                                                2-mercaptobenzthiazole 10 mg/l                                                to give a metallic copper image.                                              ______________________________________                                    

                                      TABLE 1                                     __________________________________________________________________________     no.Ex.                                                                           ##STR6##                                                                                       ##STR7##                 [°C.]Tg                                                                    ##STR8##                    __________________________________________________________________________        ##STR9##        3  7       3      2      76  0.51                         8                                                                                 ##STR10##       3  7       3      2      107 0.55                         9                                                                                 ##STR11##       3  7       3      2      102.8                                                                             0.62                         10                                                                                ##STR12##       1  1       3      --     101 0.71                         __________________________________________________________________________

Examples 11-14

According to Example 9, epoxy resins are prepared from 1 milliequivalentof novolak, 3 mmol of propan-2-olamine, a mixture of 1 mmol of bisphenolA diglycidyl ether "advanced" with bisphenol A (epoxy equivalent: 901g/mol) and 6 mmol of 5,5'-dimethylhydantoin N,N'-diglycidyl ether, and 3mmol of carboxylic acid hydrazide of the formula ##STR13## The procedureis otherwise as in Examples 7-10. The results are collated in Table 2.

                  TABLE 2                                                         ______________________________________                                         Example  n          Tg (°C.)                                                                        ##STR14##                                       ______________________________________                                        11       0          84       0.40                                             12       1          76       0.52                                             13       2          75       0.61                                             14       9          72       0.64                                             ______________________________________                                    

What is claimed is:
 1. A curable composition comprising(a) at least oneepoxy resin with an average of more than one epoxy group in themolecule, (b) an epoxy resin hardener if necessary, (c) at least oneanthraquinone of formula I ##STR15## wherein X is the group --CR² R³ --,where R² is H, --CN or C₁ -C₅ -alkyl and R³ is H or --CN, R¹ is H or C₁-C₅ -alkyl and R is a direct bond or linear or branched C₁ -C₁₈-alkylene which, alone or together with the --CR² R³ -- group, can beinterrupted by one or more --O-- when R² and/or R³ are not --CN, itbeing possible for the group -X-R- additionally to be a direct bond, and(d) at least one primary or secondary aliphatic amine containing atleast one hydroxyl group in the aliphatic radical.
 2. A compositionaccording to claim 1, which contains(c) the anthraquinone of formula Iin an amount of 0.1-1 mol/kg of epoxy resin, and (d) the amine in anamount of 0.1-1.2 mol/kg of epoxy resin.
 3. A composition according toclaim 1, which contains glycidylated novolaks, hydantoins, aminophenols,bisphenols or aromatic diamines as epoxy resins.
 4. A compositionaccording to claim 3, wherein the epoxy resin is an epoxidized cresolnovolak, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether"advanced" with bisphenol A, 5,5-dimethylhydantoin N,N'-bisglycide,1,3-bis(N,N'-diglycidyl-5,5-dimethylhydanto-4-yl)-2-glycidoxypropane,p-aminophenol triglycide, diaminodiphenylmethane or mixtures thereof. 5.A composition according to claim 1, wherein the hardener (b) is anovolak, a polyamine or a polycarboxylic acid anhydride.
 6. Acomposition according to claim 1, wherein the amine of component (d) hasthe formula IV ##STR16## wherein R⁵ is H, linear or branched C₁ -C₁₈-alkyl, C₃ -C₇ -cycloalkyl, C₆ -C₁₀ -aryl, C₇ -C₁₈ -alkaryl, C₇ -C₁₇-aralkyl, C₈ -C₁₈ -alkaralkyl or the group --C_(y) H_(2y+1-x) (OH)_(x),x is a number from 1 to 3 and y is a number from 2 to 12, it beingpossible for the group C_(y) H_(2y) to be interrupted by one or more--O-- or --NR⁵ --.
 7. A composition according to claim 1, wherein, informula IV, R⁵ is H, y is a number from 2 to 7 and x is a number from 1to
 3. 8. A cured composition consisting of(a) at least one epoxy resinwith an average of more than one epoxy group in the molecule, (b) anepoxy resin hardener if necessary, (c) at least one anthraquinone offormula I according to claim 1, it being possible for the group --XR--additionally to be a direct bond, and (d) at least one primary orsecondary aliphatic amine containing at least one hydroxyl group in thealiphatic radical.
 9. A process for the preparation of a metalliccoating or image on an epoxy resin, in which a composition according toclaim 1 is cured, then exposed over the surface or through a master andfinally treated with a metal deposition bath.